Monoazo dyestuff mixtures to dye polyester yellow

ABSTRACT

A monoazo dyestuff mixture which comprises 90-30% by weight of a monoazo dyestuff of the general formula [II]: ##STR1## wherein R 2  is C 3-6  alkyl, C 1-4  alkoxyalkyl, phenoxyalkyl or aralkyl and 10-70% by weight of a monoazo dyestuff of the formula [III]: ##STR2##

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to monoazo dyestuff mixtures for polyesterfibers. More specifically, it relates to monoazo dyestuff mixtures whichdye polyester fibers in yellow colors excellent in various fastnessproperties, in particular, light fastness, sublimation fastness, washingfastness, perspiration fastness and water fastness, and which are alsoexcellent in heat resistance and alkali discharge printing properties.

2. Description of the Prior Art

Recently, an alkali discharge printing process has been increasinglyfrequently carried out as a new dyeing process for polyester fibers. Theprinciple of the alkali discharge printing is to hydrolyze a dyestuffwith alkali, thereby depriving it of its affinity to polyester fibers.

Therefore, the dyestuffs intended for that purpose contained carboxylateester groups, hydroxyl groups etc. which had great hydrophilicproperties and were easily reactive with alkali in their backbonestructure, and for that reason, they had a disadvantage that their wetfastness, such as washing fastness, perspiration fastness, waterfastness etc. and also heat resistance were poor.

Heretofore, dyestuffs having similar structures to those of thisinvention are known from Japanese Patent Publication No. 5456/1978 andJapanese Patent Application Laid-open No. 49661/1982, but it has beendesired that their wet fastness and heat resistance be more improvedwhile good alkali discharge printing properties be maintained.

Previously, the present inventors had invented dyestuffs of the generalformula [I] below which dye polyester fibers in yellow colors andprovide dyed cloths excellent in various fastness properties such aslight, sublimation, wet and the like fastness properties and had filedan application for a patent (Japanese Patent Application No.10229/1983): ##STR3## wherein R¹ represents an alkyl group, aphenoxyalkyl group, an alkoxyalkyl group or an aralkyl group.

However, when used singly, these dyestuffs had been expected to befurther improved in an aspect of dyeing characteristics such as dyeingaffinity, temperature dependence at the time of dyeing, build-upproperties etc. although their various fastness properties such aslight, sublimation, wet and the like fastness properties, and alkalidischarge printing properties were excellent. A further study has beencarried out to improve dyeing characteristics such as dyeing affinity,temperature dependence at the time of dyeing, build-up properties etc.of the yellow monoazo dyestuffs of the above general formula [I], and,as a result, it has also been discovered that mixtures of dyestuffs ofthe general formulae [II] and [III] hereinbelow at certain mixing ratiosare excellent in the above-described dyeing characteristics whilemaintaining or even improving the above-described advantages, i.e.,various fastness properties, heat resistance, alkali discharge printingproperties.

SUMMARY OF THE INVENTION

According to an aspect of this invention, there is provided a monoazodyestuff mixture which comprises 90-30% by weight of a monoazo dyestuffof the general formula [II]: ##STR4## wherein R² is C₃₋₆ alkyl, C₁₋₄alkoxyalkyl, phenoxyalkyl or aralkyl and 10-70% by weight of a monoazodyestuff of the general formula [III]: ##STR5##

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The dyestuffs of the general formula [II] and [III] above may beproduced by coupling 4-phenoxyethoxycarbonylaniline with a pyrazolone ofthe general formula [IV]: ##STR6## wherein R is ethyl or R² as definedabove. Examples of R² in the general formula [II] above include C₃₋₆alkyl such as straight-chain or branched-chain propyl, butyl, pentyl,hexyl, C₁₋₄ alkoxyalkyl such as methoxyethyl, ethoxyethyl, butoxyethyl,phenoxyalkyl such as phenoxyethyl etc., and aralkyl such as benzyl,phenetyl etc.

The mixtures of monoazo dyestuffs of this invention may be prepared byproducing separately a monoazo dyestuff of the general formula [II]above and a monoazo dyestuff of the formula [III] above and subsequentlymixing both, or since the diazo components for the monoazo dyestuffs ofthe formulae [II] and [III] above are common to each other, they may beprepared instantaneously by using a coupling solution containingcoupling components for the dyestuffs of the formulae [II] and [III]above at a predetermined ratio at the time of coupling to prepare saidmonoazo dyestuffs.

Examples of fibers which can be dyed with the monoazo dyestuff mixturesof this invention include fibers composed of synthetic polymericmaterials such as polyesters, polyester ethers etc. or mixed spunproducts of two or more of these synthetic fibers or mixed spun productsof these fibers with natural fibers such as cotton, silk, wool etc., inparticular, fibers composed of polyesters such as polyethyleneterephthalate, a polycondensate of terephthalic acid and1,4-bis-(hydroxymethyl)cyclohexane, etc. are preferred.

Dyeing of a polyester fiber with the dyestuff of this invention may beachieved in the conventional manner, for example, by dispersing themonoazo dyestuff mixtures above in an aqueous medium using a dispersingagent such as a condensate of naphthalenesulfonic acid and formaldehyde,a higher alcohol sulfuric acid ester, a higher alkylbenzenesulfonic acidsalt etc. to prepare a dyeing bath or printing paste, and conducting dipdyeing or print dyeing. For example, where dip dyeing is conducted, byapplying a convention dyeing process, e.g., high temperature process,carrier process, thermosol process etc., polyester fibers or their mixedspun or mixed woven products can be dyed in colors excellent in fastnessproperties may be obtained. In addition, even better results maysometimes be obtained by adding an acidic substance such as formic acid,acetic acid, phosphoric acid, ammonium sulfate etc. to the dyeing bath.

This invention is more particularly described by the following examples.

EXAMPLE 1 (A) Preparation of a Monoazo Dyestuff Mixture

15.9 g of sodium carbonate was dissolved in 1500 ml of water, and 24 gof 1-phenyl-3-n-propoxycarbonylpyrazolone was added to the obtainedsolution to prepare a coupling solution.

25.7 g of 4-phenoxyethoxycarbonylaniline was dispersed in 100 g ofice-water containing 7.7 g of sodium nitrite, and the obtaineddispersion was added dropwise to 240 g of 10% by weight hydrochloricacid to prepare a diazo solution.

The above-contained diazo solution was added dropwise to the couplingsolution at 10° C. or below, and the separated crystals were filteredout and dried to produce 46.3 g of a monoazo dyestuff of the followingformula [V]: ##STR7## Thereafter, procedures similar to the proceduresto prepare the above-described coupling solution were conducted exceptthat the 1-phenyl-3-propoxycarbonylpyrazolone was replaced by 24 g of1-phenyl-3-ethoxycarbonylpyrazolone to produce 45.6 g of the monoazodyestuff of the formula [III] above of this invention.

The respective monoazo dyestuffs of the formulae [V] and [III] obtainedabove were mixed one g each to obtain a monoazo dyestuff mixture of thisinvention having a λmax (acetone) of 413 nm.

(B) Dyeing Method

0.5 g of the monoazo dyestuff mixture of this invention produced in (A)above was dispersed in 3 l of water containing 1.0 g of anaphthalenesulfonic acid-formaldehyde condensate and 2 g of a higheralcohol sulfuric acid ester to prepare a dyeing bath. 100 g of apolyester cloth was dipped in this dyeing bath to effect dyeing at 130°C. for 60 minutes, followed by soaping, washing with water and drying toobtain a yellow dyed cloth.

The obtained dyed cloth was measured for the alkali discharge printingproperties, degree of dyeing, temperature dependence and build-upproperties, and the results are given in Table 1.

EXAMPLE 2

7 g of the monoazo dyestuff of the formula [V] obtained in Example 1 and3 g of the monoazo dyestuff of the formula [III] obtained similarly weremixed to obtain a monoazo dyestuff mixture of this invention.

0.5 g of the obtained monoazo dyesuff mixture (λmax in acetone: 413 nm)was mixed with 0.5 g of a naphthalenesulfonic acid-formaldehydecondensate, and pulverized on a paint shaker to obtain a finelyparticulated dyestuff. This was then adequately mixed with a basal pastehaving the following composition:

    ______________________________________                                        Carboxymethyl cellulose type sizing agent                                                               30     g                                            Tartaric acid             0.2    g                                            Aromatic carrier          0.3    g                                            Water                     68.5   g                                            Total                     99.0   g                                            ______________________________________                                    

to obtain 100 g of a printing color paste.

A polyester cloth was print dyed with this printing color paste,provisionally dried at 100° C., then maintained in superheated steam at170° C. for 7 minutes to develop a color, soaped, washed with water anddried.

The obtained dyed cloth was measured for the alkali discharge printingproperties, degree of dyeing, temperature dependence and build-upproperties, and the results are given in Table 1.

COMPARATIVE EXAMPLES 1 and 2

Polyester cloths were dyed respectively by a printing method similar tothat described in Example 1 (B) except that the monoazo dyestuff of theformula [V] and the monoazo dyestuff of the formula [III] both obtainedin Example 1 were used singly in amounts of 0.5 g respectively, and theobtained dyed polyester cloths were measured similarly as in Example 1.The obtained results are given in Table 1.

COMPARATIVE EXAMPLE 3

A polyester cloth was dyed by a printing method similar to thatdescribed in Example 1 (B) except that 0.5 g of a monoazo dyestuffmixture obtained by mixing 2 g of the monoazo dyestuff of the formula[V] and 8 g of the monoazo dyestuff of the formula [III], both obtainedin Example 1, was used, and the obtained dyed cloth was measuredsimilarly as in Example 1. The obtained results are given in Table 1.

                  TABLE 1                                                         ______________________________________                                                                      Build-up                                        Alkali       10% o.w.f.       Properties                                      Discharge    Degree  Temperature  (10%/5%)                                    Printing     of      Dependence   Ratio to                                    Properties   Dyeing  (120° C./130° C.)                                                            Degree of                                   (Grade)      (%)     (%)          Dyeing (%)                                  ______________________________________                                        Example                                                                              5         90      90         95                                        Example                                                                              5         90      90         90                                        2                                                                             Compara-                                                                             4-5       40      50         45                                        tive                                                                          Example                                                                       1                                                                             Compara-                                                                             4-5       70      70         70                                        tive                                                                          Example                                                                       2                                                                             Compara-                                                                             4-5       60      60         65                                        tive                                                                          Example                                                                       3                                                                             ______________________________________                                    

As shown in Table 1, it is obvious that the monoazo dyestuff mixture ofthis invention has extremely excellent dyeing affinity, temperaturedependence and build-up properties and remarkably improved alkalidischarge printing properties.

EXAMPLES 3-8

Using monoazo dyestuff mixtures set forth in Table 2, polyester clothswere dyed by procedures similar to those in Example 1 (B), and theobtained dyed cloths were measured similarly as in Example 1. Theobtained results are given in Table 2.

                  TABLE 2                                                         ______________________________________                                        General Formula:                                                               ##STR8##                                                                                       10% o.w.f.                                                                                    Build-up                                                                              Temper-                                  R =                          Properties                                                                            ature                                    C.sub.2 H.sub.5 /                                                                      λmax                                                                           Hue of      Ratio to                                                                              Depend-                             Ex-  C.sub.3 H.sub.7                                                                        (Ace-   Poly- Dyeing                                                                              Degree of                                                                             ence                                am-  Ratio    tone)   ester Affin-                                                                              Dyeing  (120° C./                    ple  (Weight) (nm)    Cloth ity (%)                                                                             (%)     130° C.)                     ______________________________________                                        3    70/30    413     Yellow                                                                              85    80      91                                  4    60/40    413     "     86    90      96                                  5    35/65    413     "     88    90      92                                  6    25/75    413     "     90    88      94                                  7    20/80    413     "     92    85      90                                  8    10/90    413     "     92    80      88                                  ______________________________________                                    

EXAMPLES 9-27

Using monoazo dyestuff mixtures set forth in Table 3, polyester clothswere dyed by procedures similar to those in Example 1 (B), and theobtained dyed cloths were measured similarly as in Example 1. Theobtained results are given in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    General Formula                                                                ##STR9##                                                                                                                 Build-up                          10% o.w.f.                     Properties                                                                    Degree       (10%/5%)                                              λmax                                                                         Hue of                                                                             of  Temperature                                                                            Ratio to                                              (Acetone)                                                                           Polyester                                                                          Dyeing                                                                            Dependence                                                                             Degree of                         Example                                                                            R              (nm)  Cloth                                                                              (%) (120° C./130° C.)                                                        Dyeing (%)                        __________________________________________________________________________     9   C.sub.2 H.sub.5 /C.sub.4 H.sub.9 (n)                                                     70/30                                                                             413   Yellow                                                                             92  85       90                                10   "          60/40                                                                             "     "    90  88       90                                11   "          50/50                                                                             "     "    95  90       92                                12   "          40/60                                                                             "     "    94  88       95                                13   "          30/70                                                                             "     "    92  90       90                                14   "          20/80                                                                             "     "    92  85       88                                15   C.sub.2 H.sub.5 /C.sub.5 H.sub.11 (n)                                                    50/50                                                                             "     "                                                   16   "          30/70                                                                             "     "                                                   17   C.sub.2 H.sub.5 /C.sub.6 H.sub.13 (n)                                                    50/50                                                                             "     "                                                   18   "          30/70                                                                             "     "                                                   19   C.sub.2 H.sub.5 /C.sub.2 H.sub.4 OCH.sub.3                                               70/30                                                                             "     "    91  90       93                                20   "          50/50                                                                             "     "    96  95       96                                21   "          30/70                                                                             "     "    96  92       95                                22   C.sub.2 H.sub.5 /C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                        50/50                                                                             "     "                                                   23   C.sub.2 H.sub.5 /C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                    50/50                                                                             "     "    96  94       90                                24   "          30/70                                                                             "     "    96  92       90                                  25                                                                                ##STR10## 50/50                                                                             "     "                                                     26 "          30/70                                                                             "     "                                                     27                                                                                ##STR11## 50/50                                                                             "     "                                                   __________________________________________________________________________

COMPARATIVE EXAMPLES 4 and 5

For comparison, polyester cloths were dyed using the above-describedknown dyestuffs by procedures similar to those in Example 1, and theiralkali discharge printing properties, washing fastness, perspirationfastness, water fastness and heat resistance were measured, the resultsof which are shown in Table 4 together with the results of Example 1.

                                      TABLE 4                                     __________________________________________________________________________                                        Alkali                                                                              Fastness after                                                          Discharge                                                                           Polyurethane Finish                                                                          Heatde)                                                  Printing   Perspira- Resistance                                               Properties                                                                          Washing                                                                            tion Water                                                                              (% Re-               Dyestuff                            (Grade)                                                                             Fastness                                                                           Fastness                                                                           Fastness                                                                           maining)             __________________________________________________________________________    Known Dyestuff 1                                                                     ##STR12##                    4-5   1    1    1     60%                   Known Dyestuff 2                                                                   ##STR13##                    "     2-3  3    2-3  70                     Dyestuff Mixture of the Inven- tion (Ex- ample 1)                                  ##STR14##                    "     4-5  .sup. 5.sup.-                                                                      4-5  95                         +                                                                              ##STR15##                                                              __________________________________________________________________________

Notes

(1) Known Dyestuff 1: Described in Japanese Patent Publication No.5456/1978; and Known Dyestuff 2: Described in Japanese PatentApplication Laid-open No. 49661/1982.

(2) Alkali Discharge Printing Properties: A dyed cloth previously dyedwith the particular dyestuff was coated with a discharge printing pastecontaining sodium carbonate and polyethylene glycol (average molecularweight: 400), treated with superheated steam at a temperature of 180° C.for 7 minutes, then reducingly washed, and the whiteness of thedischarged part of the obtained dyed cloth was judged using a gray scalefor staining.

(3) Polyurethane Finishing Method: Curing was conducted using a 1%solution of Hydran F-24K at 160° C. for 2 minutes.

(4) Washing Fastness: A multi-fiber was attached to a dyed,polyurethane-finished cloth, and a washing test was conducted accordingto AATCC Method, Washing No. IIA; the staining of the nylon fiber of themulti-fiber was judged by a gray scale.

(5) Perspiration Fastness: A dyed, polyurethane-finished cloth wastested according to JIS L-0848 Method A, using a nylon cloth and a silkcloth as attached cloths, and the degree of staining of the silk clothas judged by a gray scale.

(6) Water Fastness:

A dyed, polyurethane-finished cloth was tested according to JIS L-0846Method A, except that the attached nylon cloth was replaced by a silkcloth, and the degree of staining of the silk cloth was judged by a grayscale.

(7) Heat Resistance: A dyestuff cake was mixed with anaphthalenesulfonic acid-formaldehyde condensate, and heat treated at130° C. for an hour; the percent of the remaining dyestuff after heattreatment was determined to judge the heat resistance.

    Percent of the Remaining Dyestuff=OD of the Dyestuff after Heat Treatment/OD of the Non-treated Dyestuff×100.

What is claimed is:
 1. A monoazo dyestuff mixture which comprises 90-30%by weight of a monoazo dyestuff of the general formula [II]: ##STR16##wherein R² is C₃₋₆ alkyl, C₁₋₄ alkoxyalkyl, phenoxyalkyl or aralkyl and10-70% by weight of a monoazo dyestuff of the formula [III]: ##STR17##2. The monoazo dyestuff mixture according to claim 1 wherein R² in thegeneral formula [II] is C₃₋₆ alkyl or C₁₋₄ alkoxyalkyl.
 3. The monoazodyestuff mixture according to claim 1 wherein R² in the general formula[II] is C₃₋₅ alkyl or C₁₋₄ alkoxyethyl.
 4. The monoazo dyestuff mixtureaccording to claim 1 which comprises 90-50% by weight of the monoazodyestuff of the general formula [II] and 10-50% by weight of the monoazodyestuff of the formula [III].
 5. The monoazo dyestuff mixture accordingto claim 1 which comprises 80-60% by weight of the monoazo dyestuff ofthe general formula [II] and 20-40% by weight of the monoazo dyestuff ofthe formula [III].